The Journal of Organic Chemistry
Article
K. The 1H and 13C NMR chemical shifts are reported relative to
residual solvent signals, and 31P NMR resonances are referenced to an
internal standard sample of 85% H3PO4 (δ 0.0). Coupling constants
(J) are denoted in Hz and chemical shifts (δ) in ppm. Multiplicities are
denoted as follows: s = singlet, d = doublet, m = multiplet, t = triplet.
General Procedure for the Synthesis of 5a−c. Under an
atmosphere of nitrogen, 4 (772 mg, 2.10 mmol), [G-n]-Br (for G-0,
0.59 mL, 4.83 mmol; for G-1, 1.85 g, 4.83 mmol; for G-2, 3.9 g, 4.83
mmol), and K2CO3 (2.9 g, 21.0 mmol) were mixed in DMF (25 mL).
The mixture was heated at reflux for 18 h and then cooled down to
room temperature. Solvent was distilled, and the resulted mixture was
poured into water and extracted with methylene chloride (15 mL × 3).
The organic phase was washed with water, dried over anhydrous
magnesium sulfate, and filtered. The crude products were purified by
column chromatography on silica gel (dichloromethane/petroleum
ether ∼1/1) to give compounds 5a−c.
139.1, 136.7, 131.3, 130.1, 129.7, 128.5, 128.0, 127.9, 127.7, 127.5,
126.8, 125.6, 122.9, 120.0, 106.9, 106.4, 102.0, 101.5, 94.4, 87.7, 75.4,
70.1. HR MALDI-MS for C126H100N2O14Na [(M + Na)+]: 1888.90.
General Procedure for the Self-Assembly of R1−R3. 1.0 mL
of dichloromethane-d2 was added to a mixture of triflate 6 (4.52 mg,
0.00337 mmol) and the appropriate [G-1]−[G-3] dendritic donor
precursors 1a−c (for 1a, 2.0 mg, 0.003 37 mmol; for 1b, 3.43 mg,
0.003 37 mmol; for 1c, 6.29 mg, 0.003 37 mmol). The reaction
mixture was then stirred for 1 h at room temperature. The self-
assembly was monitored by 1H and 31P NMR spectroscopy and
determined to be complete. The deuterated solvent was evaporated to
dry, and the crude product was obtained. For further purification, the
crude product was redissolved in a minimal amount of dichloro-
methane, and then n-pentane was carefully added to precipitate the
final products.
1
R1. Yield 6.26 mg (yellow solid), 96%. H NMR (CD2Cl2, 400
MHz): δ 9.09 (br, 4H), 8.72 (br, 8H), 8.30 (d, J = 8.4 Hz, 4H), 7.92
(br, 8H), 7.82 (d, J = 7.2 Hz, 4H), 7.56−7.52 (m, 24H), 7.39 (br,
12H), 5.33 (s, 8H), 1.37 (br, 48H), 1.14 (br, 72H). 31P NMR
(CD2Cl2, 162 Hz): δ 13.49 (s, 1JPt−P = 2657.3 Hz). CSI-TOF-MS, [M
− 2OTf]2+, 1784.79; [M − 3OTf]3+, 1140.53; [M − 4OTf]4+, 817.91.
Anal. Calcd for C162H192F12N4O18P8Pt4S4·H2O: C, 50.08; H, 5.03; N,
1.44. Found: C, 49.69; H, 5.23; N, 1.35.
5a. Yield 0.58 g (white solid), 65%. Rf = 0.74 (dichloromethane/
1
petroleum ether 1/1); mp 192 °C. H NMR (CDCl3, 300 MHz): δ
8.66 (s, 2H), 8.10 (d, J = 8.7 Hz, 2H), 7.69 (d, J = 6.3 Hz, 2H), 7.52−
7.49 (m, 4H), 7.43−7.36 (m, 6H), 5.27 (s, 4H). 13C NMR (CDCl3, 75
MHz): δ 143.2, 136.9, 130.6, 129.0, 128.6, 128.4, 125.4, 124.3, 120.6,
+
75.5. HR MALDI-MS for C28H20Br2O2Na [(M + Na) ]: 571.00.
5b. Yield 0.92 g (white glassy solid), 45%. Rf = 0.50 (dichloro-
1
1
R2. Yield 7.71 mg (yellow solid), 97%. H NMR (CD2Cl2, 400
methane/petroleum ether 3/1); mp 152 °C. H NMR (CDCl3, 300
MHz): δ 9.10 (d, J = 10.4 Hz, 4H), 8.71 (br, 8H), 8.28 (d, J = 8.4 Hz,
4H), 7.92 (br, 8H), 7.81 (d, J = 8.0 Hz, 4H), 7.56−7.50 (m, 16H),
7.35−7.31 (br, 40H), 6.77 (s, 8H), 6.55 (s, 4H), 5.25 (s, 8H), 4.94 (s,
16H), 1.37 (br, 48H), 1.15−1.14 (m, 72). 31P NMR (CD2Cl2, 162
MHz): δ 8.67 (d, J = 1.5 Hz, 2H), 8.08 (d, J = 8.7 Hz, 2H), 7.69 (d, J =
9.0 Hz, 2H), 7.37−7.29 (m, 20H), 6.74 (d, J = 2.1 Hz, 4H), 6.57 (t, J
= 2.1 Hz, 2H), 5.18 (s, 4H), 4.93 (s, 8H). 13C NMR (CDCl3, 75
MHz): δ 160.1, 143.1, 139.3, 136.7, 130.7, 129.1, 128.6, 128.3, 128.0,
127.5, 125.5, 124.3, 120.7, 106.9, 101.9, 75.3, 70.1. HR MALDI-MS for
C56H44Br2O6Na [(M + Na)+]: 995.10.
1
Hz): δ 13.31 (s, JPt−P = 2666.5 Hz). CSI-TOF-MS, [M − 3OTf]3+,
1423.05; [M
−
4OTf]4 +
,
1030.04. Anal. Calcd for
C
218H240F12N4O26P8Pt4S4: C, 55.51; H, 5.13; N, 1.19. Found: C,
5c. Yield 1.45 g (white glassy solid), 38%. Rf = 0.36 (dichloro-
1
55.20; H, 5.08; N, 1.12.
methane/petroleum ether 4/1); mp 46 °C. H NMR (CDCl3, 400
1
R3. Yield 10.6 mg (yellow solid), 98%. H NMR (CD2Cl2, 400
MHz): δ 9.10 (br, 4H), 8.69 (br, 8H), 8.31 (d, J = 8.4 Hz, 4H), 7.89
(br, 8H), 7.82 (br, 4H), 7.55−7.51 (m, 16H), 7.32 (br, 80H), 6.75 (s,
8H), 6.61 (s, 16H), 6.52−6.48 (m, 12H), 5.22 (s, 8H), 4.92 (s, 32H),
4.85 (s, 16H), 1.36 (br, 48H), 1.13 (br, 72). 31P NMR (CD2Cl2, 162
MHz): δ 8.65 (s, 2H), 8.09 (d, J = 8.8 Hz, 2H), 7.69 (d, J = 6.3 Hz,
2H), 7.34−7.28 (m, 40H), 6.72 (s, 4H), 6.62 (s, 8H), 6.51 (s, 6H),
5.15 (s, 4H), 4.93 (s, 16H), 4.82 (s, 8H). 13C NMR (CDCl3, 100
MHz): δ 160.1, 160.0, 143.2, 139.4, 139.2, 136.7, 130.7, 129.1, 128.5,
128.3, 127.9, 127.5, 124.3, 120.8, 106.8, 106.4, 102.0, 101.6, 70.0, 69.9.
HR MALDI-MS for C112H92Br2O14Na [(M + Na)+]: 1843.60.
General Procedure for the Synthesis of 1a−c. Under an
atmosphere of nitrogen, 6.0 mL of THF and 3.0 mL of Et3N were
added to a mixture of 4-ethynylpyridine hydrochloride (105 mg, 0.75
mmol), compounds 4a−c (4a, 110 mg, 0.25 mmol; 4b, 216 mg, 0.25
mmol; 4c, 429 mg, 0.25 mmol), CuI (4.8 mg, 0.025 mmol), and
Pd(PPh3)4 (29 mg, 0.025 mmol). The mixture was stirred at 60 °C for
8 h. Then the solvents were removed in vacuo, and the residue was
purified by column chromatography on silica gel (dichloromethane/
acetone: ∼3/1) to give 1a−c.
1
Hz): δ 13.58 (s, JPt−P = 2660.0 Hz). CSI-TOF-MS, [M − 3OTf]3+,
1989.29; [M
− , 1454.72. Anal. Calcd for
4OTf]4 +
C
330H336F12N4O42P8Pt4S4·CH2Cl2: C, 61.17; H, 5.15; N, 0.86.
Found: C, 60.80; H, 5.03; N, 0.85.
General Procedure for the Self-Assembly of R4−R6. A mixed
solvents of CD2Cl2 and acetone-d6 (1.0 mL, v/v 2/1) was added to a
mixture of [G-1] nitrate 7a (4.86 mg, 0.00337 mmol) and [G-1]
dendritic donor precursor 1a (2.0 mg, 0.00337 mmol). The reaction
mixture was stirred for 12 h at room temperature. The self-assembly
1
was monitored by H and 31P NMR spectroscopy and determined to
be complete. The deuterated solvent was evaporated to dry, and the
crude product was obtained. For further purification, the crude
product was redissolved in a minimal amount of dichloromethane, and
then n-pentane was carefully added to precipitate the final product R4.
A similar procedure was carried out for the preparation of R5 ([G-2]
nitrate 7b, 5.47 mg, 0.002 93 mmol; [G-2] donor precursor 1b, 2.98
mg, 0.002 93 mmol) and R6 ([G-3] nitrate 7c, 5.35 mg, 0.001 97
mmol; [G-3] donor precursor 1c, 3.69 mg, 0.001 98 mmol).
1a. Yield 92 mg (pale yellow solid), 62%. Rf = 0.33 (dichloro-
1
methane/acetone 3:1); mp 175 °C. H NMR (CDCl3, 400 MHz): δ
8.87 (s, 2H), 8.66 (s, 4H), 8.26 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 7.6
Hz, 2H), 7.54−7.53 (m, 4H), 7.47 (s, 4H), 7.42−7.40 (m, 6H), 5.32
(s, 4H). 13C NMR (CDCl3, 100 MHz): δ 149.8, 144.2, 137.0, 131.4,
130.0, 129.9, 128.6, 128.4, 128.0, 126.7, 125.6, 123.0, 119.9, 94.4, 87.6,
75.7. HR EI-MS calced for C42H28N2O2, 592.2151 [M+]; found:
592.2154.
1
R4. Yield 6.65 mg (yellow solid), 97%. H NMR (CD2Cl2, 400
1b. Yield 142 mg (yellow glassy solid), 56%. Rf = 0.48
1
MHz): δ 9.16 (s, 4H), 8.69 (br, 8H), 8.28 (d, J = 8.4 Hz, 4H), 7.93
(br, 8H), 7.80 (d, J = 8.4 Hz, 4H), 7.53−7.33 (m, 44H), 7.09 (s, 2H),
6.93 (s, 4H), 6.89 (s, 2H), 5.31 (s, 8H), 5.11 (s, 8H), 1.82−1.81 (m,
48H), 1.23−1.17 (m, 72H). 31P NMR (CD2Cl2, 161.9 Hz): δ 16.29 (s,
1JPt−P = 2313.6 Hz). CSI-TOF-MS, [M − 3NO3]3+, 1295.18; [M −
4NO3]4+, 955.89. Anal. Calcd for C194H216N8O24P8Pt4·H2O: C, 56.97;
H, 5.32; N, 2.74. Found: C, 56.75; H, 5.66; N, 2.64.
(dichloromethane/acetone 4:1); mp 58 °C. H NMR (CDCl3, 400
MHz): δ 8.87 (s, 2H), 8.65 (s, 4H), 8.24 (d, J = 8.4 Hz, 2H), 7.75 (d, J
= 8.8 Hz, 2H), 7.48 (s, 4H), 7.37−7.23 (m, 20H), 6.78 (s, 4H), 6.58
(s, 2H), 5.23 (s, 4H), 4.93 (s, 8H). 13C NMR (CDCl3, 100 MHz): δ
160.2, 149.8, 144.1, 139.3, 136.7, 131.4, 130.0, 129.7, 128.6, 128.0,
127.5, 126.8, 125.6, 122.9, 119.9, 107.0, 101.9, 94.4, 87.6, 75.4, 70.1.
HR ESI-MS calced for C70H53N2O6, [M+]: 1017.3898; found:
1017.3845.
1
R5. Yield 8.03 mg (yellow solid), 95%. H NMR (CD2Cl2, 400
1c. Yield 215 mg (yellow glassy solid), 46%. Rf = 0.37
(dichloromethane/acetone 2:1); mp 56 °C. H NMR (CDCl3, 400
MHz): δ 8.86 (s, 2H), 8.64 (s, 4H), 8.25 (d, J = 8.8 Hz, 2H), 7.75 (d, J
= 9.2 Hz, 2H), 7.45 (s, 4H), 7.34−7.30 (m, 40H), 6.75 (s, 4H), 6.63
(s, 8H), 6.52 (s, 6H), 5.21 (s, 4H), 4.94 (s, 16H), 4.84 (s, 8H). 13C
NMR (CDCl3, 100 MHz): δ 160.12, 160.05, 149.8, 144.2, 139.3,
MHz): δ 9.19 (s, 4H), 8.88 (br, 8H), 8.68 (br, 4H), 8.29 (br, 8H),
8.25 (d, J = 11.6 Hz, 4H), 7.45−7.30 (m, 84H), 7.08 (s, 2H), 6.93 (s,
4H), 6.86 (s, 2H), 6.76 (s, 8H), 6.67 (s, 8H), 6.55 (br, 8H), 5.24 (s,
8H), 5.05−5.02 (m, 24H), 4.93 (s, 16H), 1.81 (br, 48H), 1.23−1.16
1
1
(m, 72H). 31P NMR (CD2Cl2, 161.9 Hz): δ 16.37 (s, JPt−P = 2303.8
Hz). CSI-TOF-MS, [M − 4NO3]4+, 1380.31. Anal. Calcd for
9667
dx.doi.org/10.1021/jo201594u|J. Org. Chem. 2011, 76, 9660−9669